Synthetic use of poly[4-hydroxy(tosyloxy)iodo]styrenes
Synthetic use of poly[4-hydroxy(tosyloxy)iodo]styrenes
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DOI：
10.1021/jo010333u
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发表时间：
2001-09-07
影响因子：
3.6
通讯作者：
Togo, H
中科院分区：
文献类型：
--
作者：
Abe, S;Sakuratani, K;Togo, H
近年来，有机高价碘化合物的研究和合成应用得到了广泛的开展。1在这些化合物中，（二乙酰氧碘）苯在有机合成中得到了很好的应用。基于（二乙酰氧基碘）苯的高用途，我们最近首次报道了聚[4-（二乙酰氧基碘）苯乙烯]在芳香族化合物的碘化反应、烷基芳基酮的1，2-芳基氧化迁移反应、对苯二酚和硫化物的氧化反应以及N-甲基（2-芳基）乙磺酰胺的自由基环化反应中的应用。2此外，聚[4-（二乙酰氧基碘代）苯乙烯]的环状用途已经确立了该化合物作为环境友好试剂的地位。在此首次报道之后，聚-[4-（二乙酰氧基碘）苯乙烯]的合成用途变得流行。3今天，[羟基（甲苯磺酰氧基）碘]苯是另一种用于有机合成的有用的高价碘试剂，类似于（二乙酰氧基碘）苯，特别是用于酮和酯的R-甲苯磺酰氧基化，烯烃的邻二甲苯磺酰氧基化，以及形成1-炔基碘鎓盐、1-烯基碘鎓盐和芳基碘鎓盐。4以聚苯乙烯（平均分子量45000）和聚（R-甲基苯乙烯）（平均分子量6200）为原料，分别合成了两种新型高分子试剂：高分子量聚[4-羟基（对甲苯磺酰氧基）碘]苯乙烯和低分子量聚{R-甲基[4-羟基（对甲苯磺酰氧基）碘]苯乙烯}。聚[4-羟基-（对甲苯磺酰氧基）碘]苯乙烯和聚{R-甲基[4-羟基（对甲苯磺酰氧基）碘]苯乙烯}分别与对甲苯磺酸一水合物反应，制得聚[4-羟基-（对甲苯磺酰氧基）碘]苯乙烯和聚{R-甲基[4-羟基（对甲苯磺酰氧基）碘]苯乙烯。通过NMR定量分析在从二乙酰氧基碘代基团交换成羟基碘代基团的交换反应中形成的乙酸。（甲苯磺酰氧基）碘基团与对甲苯磺酸一水合物在聚[4-[（二乙酰氧基碘）苯乙烯]和聚{R-甲基[4-（三氟甲基）苯基]甲基}（二乙酰氧基）碘]苯乙烯}，表明[4-（二乙酰氧基碘）]苯基向[4-羟基（甲苯磺酰氧基）碘]苯基的转化定量进行。元素分析还表明，聚苯乙烯和聚（R-甲基苯乙烯）中约80%的苯基带有羟基（甲苯磺酰氧基）碘基团，其余约20%为碘苯基。通过与[羟基-（对甲苯磺酰氧基）碘]苯的红外光谱的比较，证实了上述结果，并研究了这些聚合物固载试剂在氯仿中的溶解性。聚[4-羟基（对甲苯磺酰氧基）碘]苯乙烯和聚{R-甲基[4-羟基（对甲苯磺酰氧基）碘]苯乙烯}在15 ℃下的溶解度分别为11.0和46.4 mg/mL。具有低平均MW的聚{R-甲基[4-羟基（甲苯磺酰氧基）碘]苯乙烯}比聚[4-羟基（甲苯磺酰氧基）碘]苯乙烯更易溶于氯仿中。酮的r-甲苯磺酰氧基化。R-磺酰氧基酮是有机合成中有用的结构单元。在文献方法的基础上，研究了酮与聚[4-羟基（对甲苯磺酰氧基）碘]苯乙烯和聚{R-甲基[4-羟基（对甲苯磺酰氧基）碘]苯乙烯}的5 R-对甲苯磺酰氧基化反应，并与[羟基（对甲苯磺酰氧基）碘]苯的反应进行了比较。结果示于表1中，表明聚[4-羟基（甲苯磺酰氧基）碘]苯乙烯和聚{R-甲基[4-羟基（甲苯磺酰氧基）碘]苯乙烯}显示出与[羟基（甲苯磺酰氧基）碘]苯相同的反应性。然而，聚[4-羟基（甲苯磺酰氧基）碘]苯乙烯和聚-{R-甲基[4-羟基（甲苯磺酰氧基）碘]苯乙烯}之间的反应性没有很大的差异，尽管聚[4-羟基（甲苯磺酰氧基）碘]苯乙烯与聚-{R-甲基[4-羟基（甲苯磺酰氧基）碘]苯乙烯之间的反应性不同。
Recently, the study and synthetic use of organohypervalent iodine compounds have been extensively carried out. 1 Among these compounds,(diacetoxyiodo) benzene has been well-used in organic synthesis. On the basis of the high utility of (diacetoxyiodo) benzene, we have recently reported the first synthetic use of poly [4-(diacetoxyiodo) styrene] for the iodination of aromatics, oxidative 1, 2-aryl migration of alkyl aryl ketones, oxidation of hydroquinones and sulfides, and radical cyclization of N-methyl (2-aryl) ethanesulfonamides. 2 Moreover, the recyclic use of poly [4-(diacetoxyiodo) styrene] has established this compound as an environmentally benign reagent. After this first report, the synthetic use of poly-[4-(diacetoxyiodo) styrene] became popular. 3 Today,[hydroxy (tosyloxy) iodo] benzene is another useful hypervalent iodine reagent for organic synthesis, similar to (diacetoxyiodo) benzene, especially for the R-tosyloxylation of ketones and esters, vic-ditosyloxylation of alkenes, and formation of 1-alkynyliodonium, 1-alkenyliodonium, and aryliodonium salts. 4 Thus, two types of new polymer reagents, poly [4-hydroxy (tosyloxy) iodo] styrene (high average MW) and poly {R-methyl [4-hydroxy (tosyloxy) iodo]-styrene}(low average MW), were prepared from polystyrene (average MW) 45 000) and poly (R-methylstyrene)(average MW) 6200), respectively. Poly [4-hydroxy-(tosyloxy) iodo] styrene and poly {R-methyl [4-hydroxy (tosyloxy) iodo] styrene} were prepared by the reaction of the corresponding poly [4-(diacetoxyiodo) styrene] and poly {R-methyl [4-(diacetoxy) iodo] styrene}, respectively, with p-toluenesulfonic acid monohydrate. Quantitative analysis by NMR of the acetic acid formed in the exchange reactions from the diacetoxyiodo groups into hydroxy-(tosyloxy) iodo groups with p-toluenesulfonic acid monohydrate in poly [4-(diacetoxyiodo) styrene] and poly {R-methyl [4-(diacetoxy) iodo] styrene}, respectively, suggested that the conversion of the [4-(diacetoxyiodo)] phenyl groups to [4-hydroxy (tosyloxy) iodo] phenyl groups proceeded quantitatively. Elemental analysis also indicates that∼ 80% of the phenyl groups in polystyrene and poly (R-methylstyrene) bear a hydroxy (tosyloxy) iodo group and the other∼ 20% are iodo phenyl groups. These results were also supported by comparing the IR spectra of these polymersupported reagents with the IR spectrum of [hydroxy-(tosyloxy) iodo] benzene.The solubility of these polymer-supported reagents in chloroform, as a typical organic solvent, was then studied. The solubilities of poly [4-hydroxy (tosyloxy) iodo] styrene and poly {R-methyl [4-hydroxy (tosyloxy) iodo] styrene} are 11.0 and 46.4 mg/mL at 15 C, respectively. Poly {R-methyl [4-hydroxy (tosyloxy) iodo] styrene}, which has a low average MW, is more soluble than poly [4-hydroxy (tosyloxy) iodo] styrene in chloroform. r-Tosyloxylation of Ketones. R-Sulfonyloxy ketones are useful building blocks for organic synthesis. 5 R-Tosyloxylation of ketones with poly [4-hydroxy (tosyloxy) iodo]-styrene and poly {R-methyl [4-hydroxy (tosyloxy) iodo] styrene} was carried out, and the reactivities were compared with that of [hydroxy (tosyloxy) iodo] benzene, on the basis of the literature method. 4 The results are shown in Table 1 and suggest that poly [4-hydroxy (tosyloxy) iodo] styrene and poly {R-methyl [4-hydroxy (tosyloxy) iodo] styrene} show the same reactivity as [hydroxy (tosyloxy) iodo] benzene. However, there is not a large difference in reactivity between poly [4-hydroxy (tosyloxy) iodo] styrene and poly-{R-methyl [4-hydroxy (tosyloxy) iodo] styrene}, despite the